KR20130035236A - Anti-reflective coating composition providing enhanced scratch-resistant, anti-reflective coating film using the same and method for manufacturing the film - Google Patents

Abstract

PURPOSE: An antireflective coating composition is provided to form one or more layers only by one coating process, and to form a coating layer with improved scratch resistance. CONSTITUTION: An antireflective coating composition comprises a (meth)acrylate-based compound; a hollow particle; a polymerization initiator with a first molecular weight; a polymerization initiator with a second molecular weight larger than the first molecular weight; and a solvent. A manufacturing method of an antireflective film comprises a step of preparing the antireflective coating composition; a step of spreading the composition on one or more side of the film; a step of drying the composition; and a step of curing the composition layer.

Description

Anti-reflective coating composition that provides improved scratch resistance, anti-reflective film using same and method for manufacturing the same

The present invention relates to a composition for antireflective coating that provides improved scratch resistance, a method for producing an antireflective film using the same, and thus an antireflective film.

In general, a flat panel display device such as a PDP or LCD is equipped with an antireflection film for minimizing reflection of light incident from the outside.

As the previous antireflection film, a three-layer structure in which a hard coat layer, a high refractive index layer having a thickness of 1 μm or less, and a low refractive index layer was laminated on a light-transmissive base film was mainly used. In addition, in order to simplify the manufacturing process, a two-layer structure in which a high refractive index layer and a low refractive index layer are laminated on a base film is commercialized.

Such an antireflection film is produced using a dry method or a wet method.

Among them, the dry method laminates a low refractive index material (for example, MgF ₂ , SiO _2, etc.) into a thin film on a base film by a method such as vapor deposition, sputtering, or a high refractive index material (for example, ITO (tin dope oxide). Indium), ATO (tin-doped antimony oxide), ZnO, TiO _2, etc.) and the low refractive index material are alternately laminated. The dry method has an advantage in that an antireflection film having strong interfacial adhesion between the layers can be manufactured, but the manufacturing cost is high and it is rarely used commercially.

On the other hand, the wet method is a method for applying a coating composition containing a polymer resin, an organic solvent, and the like on a base film, and drying and curing it, it is widely used commercially low production cost compared to the dry method.

However, the wet method has a disadvantage in that the manufacturing process is complicated and the interface adhesion between the layers is weak because the wet method must separately perform a process for forming each layer, such as a hard coat layer, a high refractive index layer, and a low refractive index layer included in the antireflection film. have.

Thus, research on the development of an antireflective coating composition capable of forming a structure of two or more layers with a single wet coating has been actively conducted.

However, various problems still exist such that phase separation is not performed smoothly during application of the composition during the manufacturing process, so that the function as each layer is poor, or the scratch resistance of the low refractive index layer disposed on the surface of the film is poor.

Accordingly, the present invention is to provide a composition for anti-reflective coating that can form one or more layers with a single coating while still providing improved scratch resistance.

It is also an object of the present invention to provide a method in which the antireflection film can be produced in a more simplified manner using the composition.

In addition, the present invention is to provide an anti-reflection film produced using the composition.

According to an embodiment of the present invention,

(Meth) acrylate type compounds;

Hollow particles;

A polymerization initiator having a first molecular weight;

A polymerization initiator having a second molecular weight greater than the first molecular weight; And

menstruum

Provided is a composition for antireflective coating comprising a.

Here, the first molecular weight is less than 420, the second molecular weight may be 420 to 1000.

In addition, the composition for anti-reflective coating is a polymerization initiator having 5 to 50 parts by weight of hollow particles, 1 to 30 parts by weight of a polymerization initiator having a first molecular weight, and a second molecular weight to 100 parts by weight of a (meth) acrylate compound. It may include 1 to 20 parts by weight and 100 to 500 parts by weight of the solvent.

The (meth) acrylate-based compound may include a (meth) acrylate-based compound having a polyfunctional (meth) acrylate-based compound having a functional group of 2 to 10 and a fluorine-containing substituent. For example, the (meth) acrylate-based compound includes a (meth) acrylate-based compound having a fluorine-containing substituent and a polyfunctional (meth) acrylate-based compound having functional groups 2 to 10 in a weight ratio of 1: 10 to 300. can do.

In this case, the (meth) acrylate-based compound having a fluorine-containing substituent and the polyfunctional (meth) acrylate-based compound may be a compound having a surface energy difference of 5 mN / m or more.

On the other hand, the hollow particles included in the composition may have a number average particle diameter of 1 to 200 nm.

In addition, the hollow particles may be hollow silica particles.

The solvent included in the composition may have a dielectric constant (25 ° C.) of 20 to 30 and a dipole moment of 1.7 to 2.8.

The composition may further include inorganic fine particles having a number average particle diameter of 1 to 50 nm.

On the other hand, according to another embodiment of the present invention,

Preparing a composition for the anti-reflective coating described above; Applying the composition to at least one side of the base film; Drying the applied composition; And it provides a method of producing an anti-reflection film comprising the step of curing the dried composition layer.

In the said manufacturing method, the composition apply | coated on the base film is a 1st layer containing the polymerization initiator which has a 1st molecular weight sequentially from a base film; It can spontaneously phase separate into a second layer comprising hollow particles and a polymerization initiator having a second molecular weight.

And, drying of the composition may be performed for 0.1 to 60 minutes at a temperature of 5 to 150 ℃.

In addition, the curing of the composition may be performed for 1 to 600 seconds at an ultraviolet irradiation amount of 0.1 to 2 J / ㎠.

On the other hand, according to another embodiment of the present invention,

A first layer comprising a first (meth) acrylate-based binder and a polymerization initiator having a first molecular weight in the first (meth) acrylate-based binder and formed on a base film; And

A second (meth) acrylate-based binder, a hollow particle in the second (meth) acrylate-based binder, and a polymerization initiator having a second molecular weight greater than the first molecular weight, the second being formed on the first layer layer

There is provided an anti-reflection film comprising a.

In this case, the first (meth) acrylate-based binder contains a crosslinked polymer of a multifunctional (meth) acrylate-based compound of functional groups 2 to 10, wherein the second (meth) acrylate-based binder has a fluorine-containing substituent It may include a crosslinked polymer of a (meth) acrylate-based compound. The first and second (meth) acrylate binders may further include crosslinked copolymers of a multifunctional (meth) acrylate compound having a functional group of 2 to 10 and a (meth) acrylate compound having a fluorine-containing substituent, respectively. It may include.

In addition, the thickness of the first layer may be 2 to 15 μm, and the thickness of the second layer may be 100 to 200 nm.

The antireflective coating composition according to the present invention can form one or more layers in one coating by spontaneous phase separation, which enables the production of antireflective films in a more simplified manner. In particular, the antireflection film prepared using the composition can maintain more improved interlayer interfacial adhesion and scratch resistance, can exhibit excellent antireflection effect, and can be preferably applied to antireflection films such as display devices.

Hereinafter, a composition for antireflective coating according to embodiments of the present invention, an antireflective film using the same, and a method of manufacturing the same will be described.

Prior to this, some terms are defined as follows unless explicitly stated throughout the present specification.

First, 'hollow particles' may refer to particles having a form in which empty spaces exist on the surface and / or inside of organic or inorganic fine particles. For example, 'hollow silica particles' may be hollow particles derived from a silicon compound or an organosilicon compound, and may refer to particles having a void space on the surface and / or inside of the silica particles.

In addition, potential energy to minimize free surface area is called 'surface energy' and reduced surface energy per unit surface area is defined as 'surface tension'. In other words, the surface tension and the surface energy indicate the degree to minimize the surface, it is an index unit representing the same or equivalent physical properties.

In addition, "(meth) acrylate" is defined as collectively referred to as acrylate (meth) or methacrylate (methacrylate). In addition, such a '(meth) acrylate' may be defined as not having a fluorine-containing substituent, and to distinguish from this, a compound having a fluorine-containing substituent may be referred to as a (meth) acrylate compound having a fluorine-containing substituent. Can be.

In addition, the term "coating layer" means a composition layer formed by applying (coating) a composition for antireflection coating described below on a predetermined base film.

In addition, the term 'phase separation' means that a difference is formed in the distribution of specific components included in the composition due to differences in density, surface tension, or other physical properties of the components. Here, when the coating layer is phase-separated, it may be divided into at least two layers based on whether a specific component is distributed, for example, the distribution of hollow particles.

In addition, the term 'hard coat layer' or 'high refractive index layer' refers to a layer having a relatively high refractive index and substantially no distribution of hollow particles in relation to a low refractive index layer, which will be described later. It means a layer (lower coating layer) located below the refractive index layer. Here, the meaning that the hollow particles are not substantially distributed is defined to include less than 1% by weight based on the total content of the hollow particles included in the composition.

In addition, the "low refractive index layer" is a layer having a relatively low refractive index and a high distribution ratio of hollow particles in relation to the above-described hard coat layer or high refractive index layer, and is based on the distance from the base film to the hard coat layer or high layer. It means a layer (upper coating layer) positioned above the refractive index layer.

In addition, terms including an ordinal number such as 'first' or 'second' may be used to describe various components throughout the specification, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may also be referred to as the second component, and similarly, the second component may also be referred to as the first component.

On the other hand, the inventors of the present invention in the course of repeated studies on the composition for anti-reflective coating, when forming an anti-reflection film while inducing spontaneous phase separation using a predetermined composition described later, excellent anti-reflection effect and interlayer interface adhesion Together, it was found that it is possible, in particular, to provide an antireflection film with more improved scratch resistance and completed the present invention. The excellent properties of such antireflection film may be due to the sufficient degree of curing of the surface of the coating layer by the polymerization initiator having a relatively large molecular weight that does not penetrate into the lower portion of the coating layer during the phase separation of the composition.

That is, the method of adjusting the content of the inorganic fine particles or the hollow particles, or the content of the binder was mainly applied as a method for improving the scratch resistance of the surface of the coating layer, but the effect of improving the scratch resistance was not sufficient. In addition, in general, the polymerization initiator penetrates (ie, sinks) in the direction of the base film by gravity in the drying process after application of the composition, and thus there is a problem in that the degree of curing of the upper portion of the coating layer cannot be sufficiently secured. .

In view of this, the present invention adds two or more groups of polymers having different molecular weights to the composition so that the relatively high molecular weight polymerization initiators do not penetrate into the lower part of the coating layer and remain on the upper part during phase separation of the composition, In the light curing process, it is possible to induce sufficient curing of the top of the coating layer, thereby providing an antireflection film having excellent scratch resistance.

According to an embodiment of the present invention,

(Meth) acrylate type compounds;

Hollow particles;

A polymerization initiator having a first molecular weight;

A polymerization initiator having a second molecular weight greater than the first molecular weight; And

menstruum

Provided is a composition for antireflective coating comprising a.

Hereinafter, each component that can be included in the composition will be described.

( Mat ) Acrylate series  compound

First, the (meth) acrylate-based compound is a compound capable of forming a binder upon curing of the composition, a photocurable compound commonly used in the technical field to which the present invention belongs (hereinafter referred to as 'in the art') curable compound, a compound capable of forming a crosslinked polymer by an optical energy source such as ultraviolet ray) may be applied.

In particular, according to the present invention, the (meth) acrylate-based compound is a polyfunctional (meth) acryl having functional groups 2 to 10 in order to allow sufficient crosslinking polymerization to occur while more smooth phase separation can be induced upon application of the composition. (Meth) acrylate type compound which has a late compound and a fluorine-containing substituent may be included.

That is, when the multifunctional (meth) acrylate compound and the (meth) acrylate compound having a fluorine-containing substituent are mixed, spontaneous phase separation may be induced by the surface energy characteristics of the compound. In this case, the (meth) acrylate-based compound having a fluorine-containing substituent may have a surface energy of 10 to 25 mN / m, in particular the surface energy difference with the multifunctional (meth) acrylate-based compound is 5 mN / It is advantageous that more than m can achieve a smooth phase separation effect.

In addition, according to an embodiment of the present invention, the (meth) acrylate compound is a (meth) acrylate compound having a fluorine-containing substituent and the polyfunctional (meth) acrylate compound in a weight ratio of 1: 10 to 300 It is advantageous to include in terms of expression of the effect. That is, in the (meth) acrylate compound contained in the composition of the present invention, the weight ratio of the multifunctional (meth) acrylate compound to the (meth) acrylate compound having the fluorine-containing substituent is 1: 10 to 300, preferably 1: 40 to 250, more preferably 1: 50 to 200 range is advantageous in terms of inducing a smooth phase separation of the composition.

Herein, the polyfunctional (meth) acrylate-based compound has a number of (meth) acrylate-based functional groups of 2 to 10, preferably 2 to 8, more preferably 2 to 7 in terms of formation efficiency of the crosslinked polymer. It is advantageous.

Such polyfunctional (meth) acrylate-based compounds include dipentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylenepropane triacrylate, ethylene glycol diacrylate, 9,9-bis (4- (2-acryloxyethoxy) phenyl) fluorene, bis (4-methacryloxy thiophenyl) sulfide, etc. are mentioned; Preferably it may be one or more compounds selected from the group consisting of the compounds.

In addition, the (meth) acrylate-based compound having a fluorine-containing substituent, the compound satisfying the above-described surface energy characteristics may be at least one compound selected from the group consisting of

[Formula 1]

In Formula 1, R ¹ is a hydrogen group or an alkyl group having 1 ~ 6, a is an integer from 0 to 7, b is an integer from 1 to 3;

[Formula 2]

In Formula 2, c is an integer of 1 to 10;

(3)

In Formula 3, d is an integer of 1 to 11;

[Formula 4]

In Formula 4, e is an integer of 1 to 5;

[Chemical Formula 5]

In Formula 5, f is an integer of 4 to 10.

Hollow particles

On the other hand, the composition for anti-reflective coating of the present invention comprises hollow particles.

The hollow particles are collectively referred to as organic or inorganic fine particles having empty spaces on and / or inside the particles. The hollow particles may have a lower refractive index than the hollow particles and thus exhibit excellent anti-reflection characteristics. In addition, the hollow particles may be distributed mainly on the surface side of the coating layer during phase separation of the composition, or may be distributed so as to increase the distribution ratio in a direction away from the base film, thereby providing an effect of increasing film strength and scratch resistance. have.

Here, the hollow particles may have a number average particle diameter of 1 to 200 nm, preferably 5 to 100 nm, more preferably 10 to 80 nm; The shape of the particles is preferably spherical, but may be irregular.

In addition, the hollow particles may be advantageous in terms of durability and refractive index of the particles having silica as a main component (hereinafter referred to as 'hollow silica particles').

In addition, the hollow particles may be included in the composition in the form of a colloid with a solid content of 5 to 40% by weight. According to the present invention, the colloidal phase including the hollow particles may include water or an organic solvent as a dispersion medium. Herein, examples of the organic solvent in the dispersion medium include alcohols such as methanol, isopropyl alcohol, ethylene glycol and butanol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Dimethylformamide. Amides such as dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and gamma butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or mixtures thereof.

Such hollow particles may be included in an amount of 5 to 50 parts by weight, preferably 5 to 45 parts by weight, and more preferably 5 to 40 parts by weight, based on 100 parts by weight of the (meth) acrylate compound. That is, in order to ensure a minimum anti-reflection effect to the coating layer formed using the composition of the present invention, the hollow particles are contained in 5 parts by weight or more based on 100 parts by weight of the (meth) acrylate-based compound It is advantageous to be. In addition, when the hollow particles are added in an excessive amount, the thickness of the coating layer may be thickened, so that the anti-reflection effect may be lowered. In order to prevent this phenomenon, the hollow particles may be added to 100 parts by weight of the (meth) acrylate compound. It is advantageous to include up to 40 parts by weight.

polymerization Initiator

On the other hand, the composition for anti-reflective coating of this invention contains the polymerization initiator which has a 1st molecular weight, and the polymerization initiator which has a 2nd molecular weight larger than a 1st molecular weight.

According to the present invention, despite the influence of gravity upon phase separation of the composition, the polymerization initiator having a second molecular weight having a relatively high molecular weight does not erode into the binder under the coating layer, and remains on the coating layer. Thereby, sufficient curing of the top of the coating layer can be induced during the curing of the phase-separated coating layer, thereby enabling the provision of an antireflection film having more improved scratch resistance.

That is, in general, in the drying process after application of the composition, the polymerization initiator penetrates (ie, sinks) in the direction of the base film by gravity, and thus there is a problem in that the degree of curing of the upper portion of the coating layer cannot be sufficiently secured. .

In view of this, the composition according to the present invention enables the provision of an antireflection film having improved scratch resistance by the above-described action, as it includes two or more groups of polymerization initiators having different molecular weights.

According to the present invention, the molecular weight range of the polymerization initiator is determined in consideration of the type and content of the (meth) acrylate-based compound used, whether or not the composition can penetrate into the high refractive index layer (lower coating layer) during phase separation of the composition. desirable. According to one embodiment of the present invention, the first molecular weight may be less than 420, and the second molecular weight may be 420 to 1000; Preferably, the first molecular weight may be less than 420 and the second molecular weight may be between 430 and 950; More preferably, the first molecular weight may be less than 420, and the second molecular weight may be 440 to 900. That is, according to the present invention, the polymerization initiator included in the composition, based on the molecular weight of about 420, it may be preferable to realize that the effect is to include less than and more than that at the same time. If any one of these is not satisfied, evenly curing of the entire coating layer may not be achieved, and thus formation of an antireflection film having improved scratch resistance may not be expected.

Meanwhile, as long as the polymerization initiator satisfies the above-described molecular weight range, a polymerization initiator conventional in the art may be applied regardless of the kind of the specific compound.

The polymerization initiator having the first molecular weight may be included in an amount of 1 to 30 parts by weight, preferably 1 to 25 parts by weight, and more preferably 1 to 20 parts by weight, based on 100 parts by weight of the (meth) acrylate compound. have. That is, in the present invention, the polymerization initiator having the first molecular weight has a relatively small molecular weight, so that it can penetrate into the lower part of the coating layer (first layer, high refractive index layer) during phase separation of the composition. Therefore, in order to sufficiently cure the lower portion of the coating layer, the polymerization initiator having the first molecular weight is advantageously included 1 part by weight or more based on 100 parts by weight of the (meth) acrylate compound. In addition, when an excessive amount of the polymerization initiator is included, the amount of the remaining polymerization initiator may increase, thereby reducing physical properties such as abrasion resistance of the coating layer. In order to prevent this, the polymerization initiator having the first molecular weight may have a weight of 100 (meth) acrylate-based compound. It is advantageous to include up to 30 parts by weight relative to the part.

The polymerization initiator having the second molecular weight may be included in an amount of 1 to 20 parts by weight, preferably 1 to 15 parts by weight, and more preferably 2 to 15 parts by weight, based on 100 parts by weight of the (meth) acrylate compound. have. That is, in the present invention, the polymerization initiator having the second molecular weight has a relatively large molecular weight so that it does not penetrate into the lower portion (first layer, high refractive index layer) of the coating layer during phase separation of the composition, and the upper portion (second layer, low Refractive index layer). Therefore, in order to express the minimum degree of hardening improvement required on the coating layer, the polymerization initiator having the second molecular weight may include 1 part by weight or more based on 100 parts by weight of the (meth) acrylate compound. It is advantageous. In addition, when the excessive amount of the photoinitiator is added, the physical properties of the coating layer such as wear resistance may be lowered. In order to prevent this, the polymerization initiator having the second molecular weight is 20 parts by weight or less based on 100 parts by weight of the (meth) acrylate compound. It is advantageous to be included.

Thus, in addition to the method of providing the molecular weight difference of a polymerization initiator, the method of using the polymerization initiator which has the solubility of a different range can also be applied. However, the solubility of the polymerization initiator is one of physical properties that can ultimately be affected by the molecular weight of the polymerization initiator, the polymerization initiator having a relatively high molecular weight has a relatively low solubility so that the amount that can be eroded to the bottom of the coating layer A small, relatively large amount may be distributed on top of the coating layer to induce sufficient hardening of the surface. In addition, it is a matter of course that the present invention may be embodied in other forms by applying other physical properties that may directly or indirectly be influenced by the molecular weight of the polymerization initiator or similar properties.

menstruum

On the other hand, the composition for anti-reflective coating of the present invention contains a solvent.

As the solvent, those conventional in the art may be used within a range that does not adversely affect the physical properties of the composition. However, according to the present invention, it is preferable that the solvent has a dielectric constant (25 ° C.) of 20 to 30 and a dipole moment of 1.7 to 2.8 in terms of inducing smooth phase separation of the composition.

Non-limiting examples of a solvent that satisfies the above physical property range may be methyl ethyl ketone, ethyl acetate, acetyl acetone, and the like. In addition to the solvent that satisfies the physical property range, one or more selected from the group consisting of isobutyl ketone, methanol, ethanol, n-butanol, i-butanol, and t-butanol may be further included. Can be. However, the solvent that satisfies the dielectric constant and dipole moment range is more preferably 60% by weight based on the total weight of the solvent in terms of inducing a smooth phase separation of the composition.

Such a solvent may be included in an amount of 100 to 500 parts by weight, preferably 100 to 450 parts by weight, and more preferably 100 to 400 parts by weight based on 100 parts by weight of the (meth) acrylate compound. That is, when coating of the composition is poor in flowability may cause defects such as streaks in the film, in order to impart the minimum flowability required for the composition, the solvent is a (meth) acrylate-based compound It is advantageous to include 100 parts by weight or more based on 100 parts by weight. In addition, when the excessive amount of the solvent is lowered, the solid content may be lowered, so that defects may occur during the drying and curing process. Do.

Inorganic Particles and Other Ingredients

In addition, the composition for anti-reflective coating of this invention may further contain an inorganic fine particle as needed. The inorganic fine particles may be distributed throughout the coating layer in the drying process after application of the composition, and in particular, further increases the film strength to impart an effect of improving the rubbing resistance.

In this case, as the inorganic fine particles, those conventional in the art may be used, and preferably silica particles. However, unlike the above-mentioned hollow particles, the inorganic fine particles do not have to be hollow, and may be amorphous.

In addition, the particle diameter of the inorganic fine particles may be determined in consideration of compatibility with the solvent, light transmittance, haze characteristics, and the like, and preferably, the number average particle diameter may be 1 to 50 nm.

In addition, the composition for anti-reflective coating of the present invention may further include components commonly used in the art in addition to the above-described components according to the physical properties to be applied to the anti-reflection film. For example, the composition of the present invention may further include additives such as surfactants, leveling agents, thickeners, silane coupling agents and the like as necessary. At this time, the content of the additive is not particularly limited because it can be determined in various ways within the range of not lowering the physical properties of the composition according to the present invention.

On the other hand, according to another embodiment of the present invention,

Preparing a composition for the anti-reflective coating described above;

Applying the composition to at least one side of the base film;

Drying the applied composition; And

Curing the dried composition layer

There is provided a method of manufacturing an antireflection film comprising a.

That is, the method for producing an antireflective film according to the present invention may be performed in the order of coating, drying and curing the coating composition on a base film according to a conventional method, except for using the above-described composition. In particular, as the production method according to the present invention is carried out using the above-described composition, one or more layers may be formed by spontaneous phase separation even with a single coating upon application of the composition, thus making the interlayer interface a simpler process. An antireflection film having excellent adhesion can be produced. Furthermore, as the production method according to the present invention is carried out using the above-described composition, curing of each layer formed by spontaneous phase separation can be sufficiently induced, thereby providing an antireflection film having excellent scratch resistance. do.

This manufacturing method of the present invention can be carried out according to the conventional wet coating method using the composition described above.

According to one embodiment of the present invention, first, the above-described antireflective coating composition is prepared, and the prepared composition is applied to at least one side of the base film.

In this case, the base film may be a transparent base film common in the art, such as triacetate cellulose, and the like, and therefore, there is no particular limitation. In addition, the method of applying the composition on the base film may use a conventional coating apparatus and method such as a wire bar.

Subsequently, the step of drying the applied composition may be performed.

The composition applied on the base film may form one or more layers by spontaneous phase separation, wherein the polymerization initiator having the first molecular weight penetrates into the lower portion of the coating layer by gravity as it has a relatively small molecular weight. In addition, the polymerization initiator having a second molecular weight having a relatively high molecular weight does not penetrate into the lower portion of the coating layer and remains at the upper portion.

That is, according to one embodiment of the present invention, the composition applied on the base film, and sequentially from the base film, the first layer comprising a polymerization initiator having a first molecular weight; It can spontaneously phase separate into a second layer comprising hollow particles and a polymerization initiator having a second molecular weight.

At this time, the phase separation process of the composition is not artificial, but is made naturally over time due to differences in molecular weight and surface energy, and the polymerization initiator having the hollow particles and the second molecular weight included in the second layer is a base film The distribution rate may tend to increase in the direction away.

Therefore, the drying step may be carried out by applying the composition on a base film and then left to dry under certain conditions. However, in order to promote phase separation of the composition in the drying step and to allow sufficient phase separation, the drying of the composition is preferably performed for 0.1 to 60 minutes at a temperature of 5 to 150 ℃. Through this drying step, it is confirmed that the phase separation into the upper portion of the coating layer (second layer, low refractive index layer) containing the hollow particles and the lower portion of the coating layer (first layer, high refractive index layer) substantially free of hollow particles. Can be.

Subsequently, curing of the dried composition layer may be performed.

The curing step is a step of inducing a polymerization reaction by irradiating light to the composition layer dried in a phase-separated state, thereby curing the composition layer, it can be carried out under photocuring reaction conditions conventional in the art. However, according to the present invention, in order to induce a sufficient curing reaction, the curing of the composition is preferably carried out for 1 to 600 seconds at an ultraviolet irradiation amount of 0.1 to 2 J / ㎠.

On the other hand, in addition to the above-described steps, the method for producing an anti-reflection film according to the present invention may be further performed before or after each step in the art, the present invention only by the above steps The manufacturing method of is not limited.

On the other hand, according to another embodiment of the present invention, an anti-reflection film formed using the above-described composition may be provided.

An example of the antireflection film which concerns on this invention contains the 1st (meth) acrylate type binder and the polymerization initiator which has a 1st molecular weight in the said 1st (meth) acrylate type binder, and is formed on the base film First floor; And a polymerization initiator having a second (meth) acrylate-based binder, a hollow particle in the second (meth) acrylate-based binder, and a second molecular weight greater than the first molecular weight, the agent being formed on the first layer. It may comprise two layers.

Here, the first molecular weight may be less than 420, the second molecular weight may be 420 to 1000.

In such anti-reflection film, the first layer formed on the base film can act as a high refractive index layer exhibiting a refractive index of about 1.5 or more, while serving as a hard coat layer of the antireflection film. The first layer may include a first (meth) acrylate-based binder and a polymerization initiator having a first molecular weight in the binder. In addition, the first (meth) acrylate-based binder may include a crosslinked polymer of a multifunctional (meth) acrylate-based compound having functional groups 2 to 10, and may further include inorganic fine particles in the binder.

In addition, the second layer in contact with and covering the first layer has substantially all or most of the hollow particles (eg, at least about 97% by weight, or at least about 99% by weight) resulting in a low distribution of the antireflection film. It can act as a refractive index layer. This second layer can exhibit a low refractive index of about 1.45 or less, resulting in a suitable antireflection effect. The second layer may include a second (meth) acrylate-based binder, a hollow particle in the binder, and a polymerization initiator having a second molecular weight greater than the first molecular weight. The second (meth) acrylate binder may include a crosslinked polymer of a (meth) acrylate compound having a fluorine-containing substituent, and may further include inorganic fine particles in the binder.

In addition, the first and second (meth) acrylate-based binders are cross-linked copolymers of a multifunctional (meth) acrylate compound having a functional group of 2 to 10 and a (meth) acrylate compound having a fluorine-containing substituent, respectively. It may include. In this case, the crosslinked copolymer included in the first (meth) acrylate-based binder may have a predetermined region of the first layer, for example, about 5 to 50% of the depth of the first layer based on the interface between the first layer and the second layer. Or up to about 4 to 45% deep, or up to about 5 to 40% deep. In addition, the crosslinked copolymer included in the first binder of the first layer may be included to increase the distribution gradient in the direction of the second layer.

As such the crosslinked copolymer is distributed with a distribution gradient to a predetermined depth of the first layer, the interfacial adhesion between the first layer and the second layer can be improved more, and the hollow particles included in the second layer are densely distributed. Can be.

At this time, the thickness of the first layer may be 2 to 15 ㎛, preferably 2 to 15 ㎛, more preferably 2 to 10 ㎛ in consideration of optical properties and mechanical properties. In addition, the thickness of the second layer may be 100 to 200 nm, preferably 100 to 180 μm, more preferably 100 to 160 nm in consideration of antireflection characteristics and the like. In addition, as the antireflection film of the present invention is manufactured using a composition including a polymerization initiator that satisfies a specific molecular weight range, the degree of curing of the second layer may be sufficiently secured, and thus, more improved scratch resistance may be exhibited. .

In the above-described antireflection film, the first layer is a layer having a higher refractive index than the second layer serving as the low refractive index layer, and may have a refractive index of about 1.5 to 1.58, or about 1.5 to 1.57, or about 1.51 to 1.56. have. In addition, the second layer may have a refractive index of about 1.1 to 1.45, or about 1.15 to 1.43, or about 1.2 to 1.42.

In addition, the anti-reflection film of another embodiment described above exhibits excellent anti-reflection properties such that the reflectance is about 0.5 to 4%, or about 0.8 to 3%, or about 1 to 2%, so that various displays such as PDP, CRT, or LCD It can be suitably applied as an antireflection film in the apparatus.

Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

Example  One

(Production of antireflective coating composition)

A (meth) acrylate compound having a fluorine-containing substituent (trade name: OPTOOL AR110, 15 wt% solids, MIBK solvent, manufacturer: DAIKIN) and pentaerythritol hexaacrylate, a polyfunctional (meth) acrylate compound, are 1:80. A photocurable compound was prepared by mixing at a weight ratio of.

Based on 100 parts by weight of the photocurable compound;

About 18.7 parts by weight of hollow silica (manufacturer: Catalytic Chemical, trade name: MIBK-sol);

Darocur 1173 (molecular weight: about 164.2, manufacturer: Ciba Chemical) about 1 part by weight, Irgacure 184 (molecular weight: about 204.3, manufacturer: Ciba Chemical) about 6 parts by weight, Irgacure 819 (molecular weight: about 418.46, manufacturer) : Ciba Chemical) about 2 parts by weight, and about 1 part by weight of Irgacure 907 (molecular weight: 279.4 by Ciba Chemical);

About 5 parts by weight of OXE-01C (molecular weight about 440, manufactured by Ciba Chemical) as a polymerization initiator having a second molecular weight greater than the first molecular weight; And

As a solvent, 164 parts by weight of methyl ethyl ketone, 23 parts by weight of acetyl acetone, 23 parts by weight of ethanol, and 23 parts by weight of n-butanol were uniformly mixed to prepare a composition for antireflection coating.

(Manufacture of antireflection film)

Using the wire bar (9), the antireflective coating composition was applied to a triacetate cellulose film (thickness of 80 µm). It was dried in an oven at 90 ° C. for 2 minutes, and then irradiated with UV of 200 mJ / cm 2 for 5 seconds to cure the composition.

This gave a film having a thickness of the antireflective coating layer of about 3 μm (the thickness of the low refractive index layer containing hollow particles: about 150 nm).

Example  2

(Production of antireflective coating composition)

A (meth) acrylate compound having a fluorine-containing substituent (trade name: OPTOOL AR110, 15 wt% solids, MIBK solvent, manufacturer: DAIKIN) and pentaerythritol hexaacrylate, a polyfunctional (meth) acrylate compound, are 1:80. A photocurable compound was prepared by mixing at a weight ratio of.

Based on 100 parts by weight of the photocurable compound;

About 10.9 parts by weight of hollow silica (manufacturer: Catalytic Chemical, trade name: MIBK-sol);

Darocur 1173 (molecular weight: about 164.2, manufacturer: Ciba Chemical) about 1 part by weight, Irgacure 184 (molecular weight: about 204.3, manufacturer: Ciba Chemical) about 6 parts by weight, Irgacure 819 (molecular weight: about 418.46, manufacturer) : Ciba Chemical) about 2 parts by weight, and about 1 part by weight of Irgacure 907 (molecular weight: 279.4 by Ciba Chemical);

About 5 parts by weight of R38.4 (molecular weight: about 803.9, manufactured by LG Chemical) as a polymerization initiator having a second molecular weight greater than the first molecular weight;

As a solvent, 164 parts by weight of methyl ethyl ketone, 23 parts by weight of acetyl acetone, 23 parts by weight of ethanol, and 23 parts by weight of n-butanol were uniformly mixed to prepare a composition for antireflection coating.

(Manufacture of antireflection film)

Except for using the composition, according to the anti-reflection film production method of Example 1 to a film having a thickness of the anti-reflective coating layer of about 3 ㎛ (the thickness of the low refractive index layer containing hollow particles: about 140 nm) Prepared.

Example  3

(Production of antireflective coating composition)

A (meth) acrylate compound having a fluorine-containing substituent (trade name: OPTOOL AR110, 15 wt% solids, MIBK solvent, manufacturer: DAIKIN) and pentaerythritol hexaacrylate, a polyfunctional (meth) acrylate compound, are 1:80. A photocurable compound was prepared by mixing at a weight ratio of.

Based on 100 parts by weight of the photocurable compound;

About 10.9 parts by weight of hollow silica (manufacturer: Catalytic Chemical, trade name: MIBK-sol);

As a polymerization initiator having a first molecular weight, about 1 part by weight of Darocur 1173 (molecular weight: about 164.2, manufacturer: Ciba), about 6 parts by weight of Irgacure 184 (molecular weight: about 204.3, manufacturer: Ciba), Irgacure 819 (molecular weight: about 418.46, manufacturer: Ciba) ) About 2 parts by weight, and about 1 part by weight of Irgacure 907 (molecular weight about 279.4 by Ciba);

About 5 parts by weight of TAZ-110 (molecular weight about 448, manufactured by Midori Kagaku) as a polymerization initiator having a second molecular weight greater than the first molecular weight;

As a solvent, 164 parts by weight of methyl ethyl ketone, 23 parts by weight of acetyl acetone, 23 parts by weight of ethanol, and 23 parts by weight of n-butanol were uniformly mixed to prepare a composition for antireflection coating.

(Manufacture of antireflection film)

Except for using the composition, according to the anti-reflection film production method of Example 1 to a film having a thickness of the anti-reflective coating layer of about 3 ㎛ (the thickness of the low refractive index layer containing hollow particles: about 140 nm) Prepared.

Comparative example  One

(Production of antireflective coating composition)

A (meth) acrylate compound having a fluorine-containing substituent (trade name: OPTOOL AR110, 15 wt% solids, MIBK solvent, manufacturer: DAIKIN) and pentaerythritol hexaacrylate, a polyfunctional (meth) acrylate compound, are 1:80. A photocurable compound was prepared by mixing at a weight ratio of.

Based on 100 parts by weight of the photocurable compound;

About 10.9 parts by weight of hollow silica (manufacturer: Catalytic Chemical, trade name: MIBK-sol);

As a polymerization initiator with a molecular weight of less than 420, about 1.5 parts by weight of Darocur 1173 (molecular weight: about 164.2, manufacturer: Ciba), about 9 parts by weight of Irgacure 184 (molecular weight: about 204.3, manufacturer: Ciba), Irgacure 819 (molecular weight: about 418.46, manufacturer: Ciba) About 3 parts by weight, and about 1.5 parts by weight of Irgacure 907 (molecular weight about 279.4 by Ciba);

As a solvent, 164 parts by weight of methyl ethyl ketone, 23 parts by weight of acetyl acetone, 23 parts by weight of ethanol, and 23 parts by weight of n-butanol were uniformly mixed to prepare a composition for antireflection coating.

(Manufacture of antireflection film)

Except for using the composition, according to the anti-reflection film production method of Example 1 to a film having a thickness of the anti-reflection coating layer of about 3 ㎛ (thickness of the low refractive index layer containing hollow particles: about 130 nm) Prepared.

Experimental Example

The following items were measured or evaluated for the antireflection films prepared through Examples 1 to 3 and Comparative Example 1, and the results are shown in Table 1 below.

1) Reflectance Measurement: After the black side of the antireflection film was treated with black, the minimum reflectance value was measured. At this time, the measurement equipment is Shimadzu's Solid Spec. A 3700 spectrometer was used.

2) Transmittance and Haze Measurement: The transmittance and Haze were measured using Murakami's HR-100.

3) Scratch resistance evaluation: The number of cases where there was a wound with a length of 1 cm or more was reciprocated 10 times at a speed of 24 m / min to steel wool, which is a load of 500 g / cm 2, on the antireflection film. . At this time, depending on the number of wounds of 1 cm or more in length, less than 3 very scratch resistance (◎), 3 or more less than 7 excellent (○), 7 or more less than 10 is normal (△), 10 If it was abnormal, it evaluated as defective (X).

Example 1 Example 2 Example 3 Example 4 Reflectance (%) 1.00 1.03 0.99 1.21 Transmittance (%) 95.8 95.9 96.2 96.2 Haze (%) 0.5 0.4 0.5 0.4 Scratch resistance ◎ ○ ◎ △

As can be seen through Table 1, the anti-reflection film according to Examples 1 to 3, compared with the anti-reflection film according to Comparative Example 1, the transmittance and Haze was confirmed to be excellent in transparency by showing the same level. .

However, the antireflection film according to Examples 1 to 3 had a lower reflectance than the antireflection film according to Comparative Example 1, and particularly a polymerization initiator having a first molecular weight and a second molecular weight larger than the first molecular weight. As prepared using the composition comprising the initiator at the same time it was confirmed that the scratch resistance of the film surface is more excellent.

Claims (22)

(Meth) acrylate type compounds;
Hollow particles;
A polymerization initiator having a first molecular weight;
A polymerization initiator having a second molecular weight greater than the first molecular weight; And
menstruum
Anti-reflective coating composition comprising a.
The method of claim 1,
The first molecular weight is less than 420, the second molecular weight is 420 to 1000 composition for antireflective coating.
The method of claim 1,
Based on 100 parts by weight of the (meth) acrylate compound,
5 to 50 parts by weight of hollow particles,
1 to 30 parts by weight of a polymerization initiator having a first molecular weight,
1 to 20 parts by weight of a polymerization initiator having a second molecular weight, and
100 to 500 parts by weight of solvent
Anti-reflective coating composition comprising a.
The method of claim 1,
The (meth) acrylate-based compound is a composition for anti-reflective coating comprising a (meth) acrylate-based compound having a multifunctional (meth) acrylate-based compound having a functional group of 2 to 10 and a fluorine-containing substituent.
The method of claim 4, wherein
The (meth) acrylate compound is an antireflective coating comprising a (meth) acrylate compound having a fluorine-containing substituent and a polyfunctional (meth) acrylate compound having a functional group of 2 to 10 in a weight ratio of 1:10 to 300. Composition.
The method of claim 4, wherein
The (meth) acrylate-based compound having a fluorine-containing substituent and the polyfunctional (meth) acrylate-based compound has a surface energy difference of 5 mN / m or more composition for antireflection coating.
The method of claim 4, wherein
The polyfunctional (meth) acrylate-based compound is dipentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylenepropane triacrylate, ethylene glycol diacrylate, 9,9-bis (4 A composition for antireflection coating, which is at least one compound selected from the group consisting of-(2-acryloxyethoxy) phenyl) fluoroene and bis (4-methacryloxy thiophenyl) sulfide.
The method of claim 4, wherein
The (meth) acrylate-based compound having a fluorine-containing substituent is at least one compound selected from the group consisting of the following formula 1 to 5 antireflection coating composition:
[Formula 1]

In Formula 1, R ¹ is a hydrogen group or an alkyl group having 1 ~ 6, a is an integer from 0 to 7, b is an integer from 1 to 3;
(2)

In Formula 2, c is an integer of 1 to 10;
(3)

In Formula 3, d is an integer of 1 to 11;
[Chemical Formula 4]

In Formula 4, e is an integer of 1 to 5;
[Chemical Formula 5]

In Formula 5, f is an integer of 4 to 10.
The method of claim 1,
The hollow particles have a number average particle diameter of 1 to 200 nm anti-reflective coating composition.
The method of claim 1,
The hollow particles are hollow silica particles antireflective coating composition.
The method of claim 1,
The solvent has a dielectric constant (25 ° C.) of 20 to 30 and a dipole moment of 1.7 to 2.8.
The method of claim 1,
The solvent is at least one compound selected from the group consisting of methyl ethyl ketone, ethyl acetate, acetyl acetone, isobutyl ketone, methanol, ethanol, n-butanol, i-butanol, and t-butanol, anti-reflective coating composition.
The method of claim 1,
The composition for anti-reflection coating further comprising inorganic fine particles having a number average particle diameter of 1 to 50 nm.
Preparing an antireflective coating composition according to claim 1;
Applying the composition to at least one side of the base film;
Drying the applied composition; And
Curing the dried composition layer
Method for producing an antireflection film comprising a.
15. The method of claim 14,
The composition apply | coated on the base film is the 1st layer which contains the polymerization initiator which has a 1st molecular weight sequentially from a base film; A method for producing an antireflection film spontaneously phase separated into a second layer comprising hollow particles and a polymerization initiator having a second molecular weight.
15. The method of claim 14,
Drying of the composition is a method for producing an anti-reflection film is carried out for 0.1 to 60 minutes at a temperature of 5 to 150 ℃.
15. The method of claim 14,
Curing of the composition is a method for producing a anti-irradiation film is carried out for 1 to 600 seconds at an ultraviolet irradiation amount of 0.1 to 2 J / ㎠.
A first layer comprising a first (meth) acrylate-based binder and a polymerization initiator having a first molecular weight in the first (meth) acrylate-based binder and formed on a base film; And
A second (meth) acrylate-based binder, a hollow particle in the second (meth) acrylate-based binder, and a polymerization initiator having a second molecular weight greater than the first molecular weight, the second being formed on the first layer layer
Anti-reflection film comprising a.
The method of claim 18,
The first (meth) acrylate-based binder includes a crosslinked polymer of the multifunctional (meth) acrylate-based compound of functional groups 2 to 10,
The second (meth) acrylate-based binder is an antireflection film containing a cross-linked polymer of a (meth) acrylate-based compound having a fluorine-containing substituent.
The method of claim 19,
The first and second (meth) acrylate-based binder further comprises a crosslinked copolymer of a multifunctional (meth) acrylate-based compound having a functional group of 2 to 10 and a (meth) acrylate-based compound having a fluorine-containing substituent, respectively. Antireflection film.
The method of claim 18,
The antireflection film having a first molecular weight of less than 420 and a second molecular weight of 420 to 1000.
The method of claim 18,
The thickness of a 1st layer is 2-15 micrometers, and the thickness of a 2nd layer is 100-200 micrometers.